Conformation and vibrational spectra of 1,5-hexadiyne (bipropargyl)

The infrared spectra of 1,5-hexadiyne (bipropargyl) as a vapour, liquid and crystalline solid and in several solvents have been recorded. Raman spectra were obtained for the liquid (including polarization measurements), the crystal and for several solutions.The data were interpreted in terms of two conformers, trans and gauche, in the vapour and liquid states and one, the trans, in the crystalline form. Interpretation of the spectra in terms of the conformational equilibria was not straightforward, and firm conclusions could not be drawn from the spectra alone. Vibrational assignments were made, supported by normal coordinate calculations.     

Preparation and properties of chlorocarbonylsulphenyl bromide,ClC(O)SBr

Chlorocarbonylsulphenyl bromide, ClC(O)SBr, was prepared from fluorocarbonyl sulphenyl bromide and BCl₃. Infrared data of the vapour, liquid and matrix-isolated ClC(O)SBr in Ne, Ar and N₂ at low temperature, together with the Raman spectrum of the liquid, suggest the existence at room temperature of only one conformer in both the vapour and liquid phases with symmetry Cs (trans with respect to the halogens). Band positions are reported for all but the out-of-plane and torsional fundamental modes. Valence force constants were calculated for the A′ species and the result is compared with the corresponding constants of related molecules. The study was completed with the characterization of the compound by mass, ultraviolet and ¹³C NMR spectra.     

Infrared studies of rotational isomerism in α-halogeno-acetamides

Infrared spectra of fluoroacetamide, chloroacetamide, and iodoacetamide have been recorded in the solid, liquid, and vapour phases in the region 4000–200 cm^?1. A complete vibrational frequency assignment of the fundamental and non-fundamental bands has been made for each of these molecules. The results show that each of these compounds exists as an equilibrium mixture of gauche and trans isomers. Enthalpy differences (ΔH) between these isomers were calculated for each of these compounds in the liquid and vapour phases. The trans form is the most stable of the rotational isomers in all three phases.     

Vibrational spectra of halogen substituted cyclopropanes—V. Trans-1,2-dichlorocyclopropane

The i.r. spectra of gaseous trans-1,2-dichlorocyclopropane were measured from 4000 to 400 cm⁻¹ and to 200 cm⁻¹ in the liquid phase. The Raman spectrum of the liquid was obtained from 4000 to 50 cm⁻¹. An assignment of all 21 normal vibrations was proposed on the basis of i.r. vapour phase band contours, Raman depolarization ratios, expected group frequencies and comparison with closely related molecules. There is excellent agreement with the normal modes previously assigned for the cis and trans isomers of the chloro, bromo and iodo analogues. The data indicate little interaction between the two CHCl moieties.     

Conformational behaviour and vibrational spectra of cyclopropyl methyl ketone and methyl cyclopropyl-carboxylate

Infrared spectra in the vapour, liquid, and crystalline states and Raman spectra in the liquid and crystalline states have been obtained for cyclopropyl methyl ketone and for methyl cyclopropylcarboxylate. In cyclopropyl methyl ketone, the dominant conformer in the liquid and vapour states, the cis, has been shown to exist exclusively in the crystal. In methyl cyclopropylcarboxylate, the conformer dominant in the liquid and vapour states has been demonstrated to exist in the crystal. Vibrational assignments are made for the ring modes and for those modes which are sensitive to conformational changes.     

Vibrational spectra and crystal structure of ethyl methyl sulfide-mercury(II) chloride complex

The crystal structure of the ethyl methyl sulfide-mercury(II) chloride complex, CH₃SCH₂CH₃· HgCl₂, has been determined by X-ray diffraction. The conformation about the CS-CC axis of the complex is trans, which is different from the conformation of crystalline ethyl methyl sulfide. The Raman and IR spectra of the complex have been measured. Observed wavenumbers of the CH₂ rocking and C-C stretching vibrations of the complex are close to those of the trans form of ethyl methyl sulfide in the liquid state, but the wavenumber of the C-S stretching vibration shifts on formation of the S-Hg bond.     

The infrared and Raman spectra of carbonyl diisocyanate

The infrared and Raman spectra of carbonyl diisocyanate have been recorded. Vibrational assignments have been made on the basis that two planar conformations are present both in the liquid and vapour phases: cis—cis and cis—trans. Simple normal coordinate calculations have been used to confirm the assignments.     

Conformational analysis,barriers to internal rotation and vibrational assignment for dimethylethylamine

The IR (50–3500 cm^?1) and Raman (20–3500 cm^?1) spectra have been recorded for gaseous and solid dimethylethylamine. Additionally, the Raman spectrum of the liquid has been recorded and qualitative depolarization values have been obtained. Due to the fact that three distinct Raman lines disappear on going from the fluid phases to the solid state, it is concluded that the molecule exists as a mixture of the gauche and trans conformers in the fluid phases with the gauche conformer being more stable and the only one present in the spectra of the unannealed solid. From the temperature study of the Raman spectrum of the liquid a rough estimate of 3.9 kcal mol^?1 has been obtained for ΔH. Relying mainly on group frequencies and relative intensities of the IR and Raman lines, a complete vibrational assignment is proposed for the gauche conformer. The potential functions for the three methyl rotors have been obtained, and the barriers to internal rotation for the two CH₃ rotors attached to the nitrogen atom have been calculated to be 3.51 and 3.43 kcal mol^?1, whereas the barrier for the CH₃ rotor of the ethyl group has been calculated to be 3.71 kcal mol^?1. The asymmetric torsional mode for the gauche conformer has been observed in both the IR and Raman spectra of the gas at 105 cm^?1 with at least one hot band at a lower frequency. Since the corresponding mode has not been observed for the trans conformer, it is not possible to obtain the potential function for the asymmetric rotation although estimates on the magnitudes of some of the terms have been made. Significant changes occur in the low-frequency IR and Raman spectra of the solid with repeated annealing; several possible reasons for these changes are discussed and one possible explanation is that a conformational change is taking place in the solid where the trans form is stabilized by crystal packing forces. These results are compared to the corresponding quantities for some similar amines.     

The vibrational spectra and rotational isomerism of monochloromethyl acetate and methyl oxalyl chloride

The IR spectra of monochloromethyl acetate and methyl oxalyl chloride have been studied for the vapour, liquid and solid states. For the first ester only one conformation is present and it has a planar arrangement of heavy atoms with the chlorine directed away from the carbonyl group and with a s-cis arrangement for the basic ester framework. For methyl oxalyl chloride, evidence is presented for the presence of two rotamers, the more stable of which is probably planar with a trans arrangement of carbonyl groups.     

Vibrational spectra and rotational isomerism of triallyl amine

The infrared spectra of triallyl amine in the vapour and liquid phases (as solutions in CS₂, CCl₄, CH₃Cl and CH₃CN), and in the solid state at low temperature were measured from 250 to 4000 cm⁻¹. The Raman spectrum of the liquid was recorded and qualitative depolarization measurements were made. It is shown that in the liquid and vapour phases the molecule exists as a mixture of at least two rotational isomers, while in the crystalline phase it assumes a single configuration having point-group symmetry C₃. A vibrational assignment for the observed bands in the infrared and Raman spectra is proposed on the basis of the C₃ point group symmetry for the more stable form of the molecule.     

Spectra and structure of phosphorus—boron compounds—XXVI. Infrared and Raman spectra,conformational stability and normal coordinate analysis of ethyldichlorophosphine-borane

The Raman (3500-10 cm⁻¹) and infrared (3500-50 cm⁻¹) spectra of solid ethyldichlorophosphine-borane, CH₃CH₂P(BH₃)Cl₂ and its deuterated analog, CH₃CH₂P(BD₃)Cl₂ have been recorded. Additionally, the infrared spectra of the gases and the Raman spectra of the liquids have been recorded and qualitative depolarization ratios have been obtained. Based on the fact that several distinct Raman lines disappear on going from the liquid to the solid state, it is concluded that the molecule exists as a mixture of the gauche and trans conformers, with the trans conformer being more stable in the liquid phase, and the only one present in the solid phase. From a temperature study of the Raman spectrum of the liquid, the enthalpy difference between the gauche and trans conformers was determined to be nearly zero. Based on Raman depolarization data, group frequencies, isotopic shift factors and infrared band contours, a complete vibrational assignment has been proposed for the trans conformer. The assignment is supported by a normal coordinate calculation which was carried out utilizing a modified valence force field to obtain the frequencies of the normal modes and the potential energy distribution. The BH₃ torsion has been observed at 188 cm⁻¹, while the BD₃ torsion was not observed. The methyl torsions in the spectra of the solids have been observed at 209 and 202 cm⁻¹ for the “light” and deuterated species, respectively. From the torsional data, barriers to internal rotation have been calculated. The asymmetric torsional mode has been observed for the trans conformer in the infrared spectra of the gas phase at 108 and 104 cm⁻¹ for the BH₃ and BD₃ species, respectively. These results are compared with similar quantities for some corresponding organophosphine—borane compounds.     

On the conformational problem in trisulphides: Preparation,properties and conformational analyses of bis(fluorocarbonyl)trisulphide,FC(O)SSSC(O)F

Bis(fluorocarbonyl)trisulphide, FC(O)SSSC(O)F, was prepared both by reaction of FC(O)SCl with H₂S and by ultraviolet irradiation of FC(O)SSC(O)F. Infrared data for the vapour, liquid and matrices (in Ar, Ne and N₂), as well as Raman, u.v. mass and ¹⁹F and ¹³C NMR spectra have been obtained and interpreted. Complementary measurements were also carried out to determine the dipole moment of the liquid substance.From these data, the most stable conformer was deduced to have a trans conformation of the FC(O) groups with respect to the SSS plane, with both CO bonds syn to the SS bonds.     

Vibrational spectra and molecular conformation of diethyl fumarate and especially the maleate

Infrared and Raman spectra of diethyl maleate and diethyl fumarate were recorded in the liquid and solid states. From the spectral changes on phase transition the known conformational equilibrium s-trans/s-cis ? s-trans/s-trans in the case of dialkyl fumarates is confirmed, and the view that dialkyl maleates exist only in a single conformation is corrected. The observation of several bands in the vCC region of IR and Raman spectra of diethyl maleate, and significant intensity shifts in this region with phase transition prove the existence of at least two conformers in liquid dialkyl maleates.     

The visible spectrum of fulvene

Vapour phase and mixed crystal of the visible band system of fulvene are reported. The spectra show several interesting features including a main progression of 660 cm^?1 corresponding to the out-of-plane methylene twisting vibration. Strong Herzberg—Teller origins together with the breadth and overall diffuseness indicate two electronic states of symmetry A₁ and B₂ may be responsible for the observed spectrum. The spectra are blue shifted in going from the vapour to mixed crystal and show sequence structure to the blue of the main bands in the vapour phase.     

Infrared and raman spectra,conformation and force field of 3-methoxy propyne

The infrared spectra of 3-methoxy propyne (CH₃OCH₂CsolutionCH) in and in the crystalline and vapour states have been studied. The Raman spectra of 3-methoxy propyne and 3-methoxy propyne- 1-d have also been measured. The spectra are relatively simple, and no significant spectral alterations are revealed on conversion from vapour, to liquid, to the crystalline state. Together with vapour phase band contours and Raman polarization measurements this indicates that there is predominantly one conformer in all three states. An assignment has been proposed, based on a gauche conformation and supported by normal coordinate analysis.     

Vibrational spectra and rotational isomerism of methyl methylsilyl sulphide

Infrared and Raman spectra of methyl methylsilyl sulphide are measured for the liquid and solid states. The fundamental vibrations are assigned and the normal vibrations calculated for two possible rotational isomers about the Si-S bond. Two different solid spectra are obtained, one corresponding to the trans form and the other to the gauche form; the liquid spectrum shows the presence of both forms. The gauche form is more stable than the trans form in the liquid state by 80 ± 50 cal mol^?1. The crystallization process indicates that the freezing and melting points of the trans form are slightly higher than those of the gauche form.     

Rotational isomer stabilities of 1,2-dichloropropane in the liquid and vapour phases from a reconsideration of available nuclear magnetic resonance and

Reconsideration of data from an earlier nuclear magnetic resonance study of 1,2-dichloropropane indicates that previously reported energy differences of the two G isomers compared to the T isomer (C-Cl bonds trans) should be reassigned for both the liquid and vapour states, i.e., so that the apparently more sterically hindered isomer with the primary chlorine atom trans to hydrogen is of lower energy than the isomer in which the chlorine atom is trans to the methyl group. Using this new assignment and the experimental average coupling constants, the trans and gauche vicinal coupling constants between the methylene and methyne protons are calculated to be 10.9 and 4.4 Hz respectively. It is further proposed that the P'H (primary chlorine trans to hydrogen) carbon-chlorine stretching vibration occurs at ca. 720 cm^?1, about 60 cm^? higher than hitherto expected.     

Conformation and vibrational spectra of 1,5-hexadiyne (bipropargyl) and 1,5-hexadiyne-1,6-d2

The infrared spectra of 1,5-hexadiyne (bipropargyl) and 1,5-hexadiyne-1,6-d₂ as vapours, liquids, as solutes in various solvents and as crystalline solids at low temperatures and at high pressures have been recorded. Raman spectra were obtained for the liquids, including semiquantitative polarization measurements, and for the low temperature crystals.The data were interpreted in terms of two conformers, anti and gauche, in the vapour and liquid state and one, the anti, in the crystalline forms. A phase transition for 1,5-hexadiyne was observed at ca. 240 K. Both the high and low temperature crystals had molecules in the anti conformer.Interpretation of the spectra in terms of conformational equilibria was facilitated by a thorough vapour phase band contour analysis. With a few exceptions, all the vibrational fundamentals for both conformers were assigned and found to be in good agreement with results from normal coordinate calculations.     

Laser photolysis study of trans→cis photoisomerization of trans-1-phenyl-2-(2-naphthyl) ethylene

The direct trans→cis photoisomerization of trans-1-phenyl-2-(2-naphthyl) ethylene (trans-PNE) in liquid solution at room temperature was studied by the nanosecond laser photolysis technique. The time-resolved S_n←S₁ and T_n←T₁ absorption spectra were observed with trans-PNE at 300 K and 77 K. The lifetime of the triplet state of trans-PNE was found to be much shorter in liquid solution at room temperature than in rigid solution at 77 K. This fact and the effect of a triplet quencher shows that the photoisomerization of trans-PNE occurs mainly via the triplet state.     

Conformational composition of meta- and ortho-fluoro(trifluoromethoxy)benzene as studied by vibrational spectroscopy

The IR spectra of o- and m-F-C₆H₄OCF₃ in the gas, liquid, and solid (glass and crystal) phases were analyzed along with the Raman spectra of these compounds in the liquid and solid (glass and crystal) phases. This investigation includes both experimental and theoretical studies of the spectra. Vibrational frequencies and normal modes for all possible stable conformers of m- and o-fluoro(trifluoromethoxy)benzene were calculated using B3LYP/cc-pVTZ harmonic quantum-chemical force fields. It was found that m-F-C₆H₄OCF₃ exists as a mixture of the orthogonal and two planar conformers in the gas, liquid, and amorphous solid (glass) phases and as one orthogonal conformer in the crystal state, while o-F-C₆H₄OCF₃ exhibits only one orthogonal conformer in every phase.